Boron-Bridged Bis-Indenyl Metallocene Catalyst Systems and Polymers Produced Therefrom

ABSTRACT

Disclosed herein are catalyst compositions containing boron bridged, bis-indenyl metallocene compounds with an alkenyl substituent. These catalyst compositions can be used for the polymerization of olefins. For example, ethylene copolymers produced using these catalyst compositions can be characterized by a density less than 0.92 g/cm 3  and a melt index greater than 25 g/10 min.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 61/905,894, filed on Nov. 19, 2013, the disclosure of which isincorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.In some end-use applications, it can be beneficial for the catalystsystem employed to facilitate efficient incorporation of a comonomerduring polymerization to produce lower density copolymers. In otherend-use applications, it can be beneficial to produce high melt flowcopolymers having lower densities. Accordingly, it is to these ends thatthe present invention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing the catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, the present invention relates toboron-bridged bis-indenyl metallocene compounds containing an alkenylsubstituent, and to catalyst compositions employing such metallocenecompounds. Catalyst compositions of the present invention that containthese boron-bridged bis-indenyl metallocene compounds can be used toproduce, for example, ethylene-based homopolymers and copolymers.

In accordance with an aspect of the present invention, disclosed anddescribed herein are boron-bridged metallocene compounds having theformula:

In formula (I), M can be Ti, Zr, or Hf; each X independently can be amonoanionic ligand; and each R independently can be H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group. In^(A) can bean indenyl group with an alkenyl substituent, and In^(B) can be anindenyl group, optionally substituted with any substituent disclosedherein.

Catalyst compositions containing the boron-bridged metallocene compoundsof formula (I) also are provided by the present invention. In oneaspect, a catalyst composition is disclosed which comprises aboron-bridged metallocene compound of formula (I) and an activator.Optionally, this catalyst composition can further comprise aco-catalyst, such as an organoaluminum compound. In some aspects, theactivator can comprise an activator-support, while in other aspects, theactivator can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer. Generally, the catalystcomposition employed can comprise any of the boron-bridged metallocenecompounds disclosed herein and any of the activators disclosed herein.Further, organoaluminum compounds or other co-catalysts also can beutilized in the catalyst compositions and/or polymerization processes.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer—in this case, an ethylene/α-olefincopolymer (e.g., an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, an ethylene/1-octene copolymer)—consistent with aspects ofthis invention can be characterized by the following properties: a meltindex of greater than or equal to about 25 g/10 min, and a density ofless than or equal to about 0.92 g/cm³. Another representative andnon-limiting ethylene copolymer described herein can have a melt indexin a range from about 25 to about 2000 g/10 min (or from about 50 toabout 2000 g/10 min, or from about 50 to about 1000 g/10 min), and adensity in a range from about 0.87 to about 0.92 g/cm³ (or from about0.88 to about 0.92 g/cm³, or from about 0.88 to about 0.915 g/cm³).These copolymers, in further aspects, can be characterized by low levelsof long chain branches (LCB), and/or by a unimodal molecular weightdistribution, and/or by a conventional short chain branch distribution(SCBD).

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distributions of thepolymers of Examples 3-7, produced with different amounts of 1-hexenecomonomer present during polymerization.

FIG. 2 presents a plot of the molecular weight distributions and shortchain branch distributions of the polymers of Examples 3-7, producedwith different amounts of 1-hexene comonomer present duringpolymerization.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) a boron bridged metallocene compound, (ii) an activator, and(iii) optionally, a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBrønsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands may include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst,” in much the sameway the term “co-catalyst” is used herein to refer to, for example, anorganoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, themetallocene compound, or the activator (e.g., activator-support), aftercombining these components. Therefore, the terms “catalyst composition,”“catalyst mixture,” “catalyst system,” and the like, encompass theinitial starting components of the composition, as well as whateverproduct(s) may result from contacting these initial starting components,and this is inclusive of both heterogeneous and homogenous catalystsystems or compositions. The terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, can be used interchangeablythroughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which can be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the melt index (ing/10 min) of a copolymer produced in an aspect of this invention. By adisclosure that the MI can be in a range from about 50 to about 1000,Applicants intend to recite that the MI can be any melt index in therange and, for example, can be equal to about 50, about 100, about 200,about 300, about 400, about 500, about 600, about 700, about 800, about900, or about 1000 g/10 min. Additionally, the MI can be within anyrange from about 50 to about 1000 (for example, from about 75 to about750), and this also includes any combination of ranges between about 50and about 1000 (for example, the MI can be in a range from about 50 toabout 250, or from about 100 to about 750). Likewise, all other rangesdisclosed herein should be interpreted in a manner similar to theseexamples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing the catalyst compositions, methodsfor using the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto boron-bridged bis-indenyl metallocene complexes containing an alkenylsubstituent, to catalyst compositions employing these metallocenecomplexes, to polymerization processes utilizing such catalystcompositions, and to the resulting olefin polymers produced from thepolymerization processes.

Boron-Bridged Metallocenes

Disclosed herein are novel boron-bridged, indenyl-indenyl metallocenecompounds containing an alkenyl substituent, and methods of making thesecompounds. In an aspect of this invention, the metallocene compounds canhave the formula:

Within formula (I), M, In^(A), In^(B), each X, and each R areindependent elements of the metallocene compound. Accordingly, themetallocene compound having formula (I) may be described using anycombination of M, In^(A), In^(B), X, and R disclosed herein.

Unless otherwise specified, formula (I) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display rac or meso isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures, unless statedotherwise.

In accordance with aspects of this invention, the metal in formula (I),M, can be Ti, Zr, or Hf. In one aspect, for instance, M can be Zr or Hf,while in another aspect, M can be Ti; alternatively, M can be Zr; oralternatively, M can be Hf.

Each X in formula (I) independently can be a monoanionic ligand. In someaspects, suitable monoanionic ligands can include, but are not limitedto, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group, —OBR¹₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR¹ ₂, or OSO₂R¹, wherein R¹is a C₁ to C₁₈ hydrocarbyl group. In another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group, aC₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, a C₁to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ to C₁₂ hydrocarbyl group. Inanother aspect, each X independently can be H, BH₄, a halide, a C₁ toC₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ to C₁₀hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ to C₁₀hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₁₀ hydrocarbyl group. In yet another aspect, each X independently canbe H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, a C₁ to C₈hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR¹ ₂,or OSO₂R¹, wherein R¹ is a C₁ to C₈ hydrocarbyl group. In still anotheraspect, each X independently can be a halide or a C₁ to C₁₈ hydrocarbylgroup. For example, both X's can be Cl.

The hydrocarbyl group which can be an X (one or both) in formula (I) canbe a C₁ to C₃₆ hydrocarbyl group, including, but not limited to, a C₁ toC₃₆ alkyl group, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkylgroup, a C₆ to C₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. Forinstance, each X independently can be a C₁ to C₁₈ alkyl group, a C₂ toC₁₈ alkenyl group, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group,or a C₇ to C₁₈ aralkyl group; alternatively, each X independently can bea C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group;alternatively, each X independently can be a C₁ to C₁₀ alkyl group, a C₂to C₁₀ alkenyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ arylgroup, or a C₇ to C₁₀ aralkyl group; or alternatively, each Xindependently can be a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, aC₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

Accordingly, in some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (I) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one aspect, each X in formula (I)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another aspect,each X in formula (I) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another aspect, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (I) independently can be a cycloalkyl group,including, but not limited to, a cyclobutyl group, a substitutedcyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group,a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group,a substituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. For example, an X in formula (I) can be a cyclopentylgroup, a substituted cyclopentyl group, a cyclohexyl group, or asubstituted cyclohexyl group. Moreover, each X in formula (I)independently can be a cyclobutyl group or a substituted cyclobutylgroup; alternatively, a cyclopentyl group or a substituted cyclopentylgroup; alternatively, a cyclohexyl group or a substituted cyclohexylgroup; alternatively, a cycloheptyl group or a substituted cycloheptylgroup; alternatively, a cyclooctyl group or a substituted cyclooctylgroup; alternatively, a cyclopentyl group; alternatively, a substitutedcyclopentyl group; alternatively, a cyclohexyl group; or alternatively,a substituted cyclohexyl group. Substituents which can be utilized forthe substituted cycloalkyl group are independently disclosed herein andcan be utilized without limitation to further describe the substitutedcycloalkyl group which can be an X in formula (I).

In some aspects, the aryl group which can be an X in formula (I) can bea phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an aspect, the aryl group can be a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (I).

In an aspect, the substituted phenyl group which can be an X in formula(I) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X in formula (I).

In some aspects, the aralkyl group which can be an X in formula (I) canbe a benzyl group or a substituted benzyl group. In an aspect, thearalkyl group can be a benzyl group or, alternatively, a substitutedbenzyl group. Substituents which can be utilized for the substitutedaralkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted aralkyl groupwhich can be an X in formula (I).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (I) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (I). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be an X in formula (I) can include, but are not limited to, amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an aspect, the hydrocarboxy group which can be an X informula (I) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (I)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl groupwhich can be an X in formula (I) can be, for instance, a methylaminylgroup (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), an n-propylaminylgroup (—NHCH₂CH₂CH₃), an iso-propylaminyl group (—NHCH(CH₃)₂), ann-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group(—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be an X in formula (I) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, each X independentlycan be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively, a C₁ to C₂₄hydrocarbylsilyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₈ hydrocarbylsilyl group. In anaspect, each hydrocarbyl(one or more) of the hydrocarbylsilyl group canbe any hydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group,a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ arylgroup, a C₇ to C₈ aralkyl group, etc.). As used herein, hydrocarbylsilylis intended to cover (mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl(—SiHR₂), and trihydrocarbylsilyl (—SiR₃) groups, with R being ahydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C₃to C₃₆ or a C₃ to C₁₈ trihydrocarbylsilyl group, such as, for example, atrialkylsilyl group or a triphenylsilyl group. Illustrative andnon-limiting examples of hydrocarbylsilyl groups which can be an X informula (I) can include, but are not limited to, trimethylsilyl,triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl,tripentylsilyl, triphenylsilyl, allyldimethylsilyl, and the like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X include, but are notlimited to, —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be an X cancomprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ toC₁₂, or C₁ to C₈ hydrocarbylaminylsilyl groups). In an aspect, eachhydrocarbyl (one or more) of the hydrocarbylaminylsilyl group can be anyhydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group,a C₇ to C₈ aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl isintended to cover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂,—N(SiHR₂)₂, and —N(SiR₃)₂ groups, among others, with R being ahydrocarbyl group.

In an aspect, each X independently can be —OBR¹ ₂ or —OSO₂R¹, wherein R¹is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁ to C₁₈hydrocarbyl group. The hydrocarbyl group in OBR¹ ₂ and/or OSO₂R¹independently can be any hydrocarbyl group disclosed herein, such as,for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₄to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈ aralkylgroup; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenylgroup, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ toC₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or aC₇ to C₈ aralkyl group.

In one aspect, each X independently can be H, BH₄, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, both X's can beH; alternatively, F; alternatively, Cl; alternatively, Br;alternatively, I; alternatively, BH₄; alternatively, a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁to C₁₈ hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In one aspect, In^(A) in formula (I) can be an indenyl group with analkenyl substituent, and In^(B) can be an indenyl group optionallysubstituted with any substituent (i.e., one or more) disclosed herein,while in another aspect, In^(A) can be an indenyl group with an alkenylsubstituent, and In^(B) can be an indenyl group that does not have analkenyl substituent. The alkenyl substituent can be at any suitableposition(s) on In^(A) that conforms to the rules of chemical valence. Insome aspects, In^(A) has only one substituent, and that one substituentis an alkenyl substituent.

In one aspect, the alkenyl substituent can be a C₂ to C₁₈ alkenyl group,i.e., any C₂ to C₁₈ alkenyl group disclosed herein. In another aspect,the alkenyl substituent can be an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, or a decenyl group. In yet anotheraspect, the alkenyl substituent can be a C₂ to C₁₂ linear or branchedalkenyl group; alternatively, a C₂ to C₈ linear or branched alkenylgroup; alternatively, a C₃ to C₁₂ linear alkenyl group; alternatively, aC₂ to C₈ linear alkenyl group; alternatively, a C₂ to C₈ terminalalkenyl group; alternatively, a C₃ to C₈ terminal alkenyl group; oralternatively, a C₃ to C₆ terminal alkenyl group.

In accordance with non-limiting aspects of this invention, In^(A) can bean indenyl group with only an alkenyl substituent, and In^(B) can be anindenyl group that does not contain any substituents; or In^(A) can bean indenyl group with an alkenyl substituent and one or more othersubstituents, and In^(B) can be an indenyl group that does not containan alkenyl substituent, but contains one or more other substituents; orIn^(A) can be an indenyl group with an alkenyl substituent and one ormore other substituents, and In^(B) can be an indenyl group that doesnot contain any substituents; or In^(A) can be an indenyl group with analkenyl substituent and one or more other substituents, and In^(B) canbe an indenyl group that contains one or more substituents.

Accordingly, In^(A) can contain a substituent (one or more) in additionto the alkenyl substituent, such as H, a halide, a C₁ to C₃₆ hydrocarbylgroup, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group. Similarly,In^(B) can contain a substituent (one or more) such as H, a halide, a C₁to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, aC₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Hence, each substituent independently can be H; alternatively, a halide;alternatively, a C₁ to C₁₈ hydrocarbyl group; alternatively, a C₁ to C₁₈halogenated hydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxygroup; alternatively, a C₁ to C₁₈ hydrocarbylsilyl group; alternatively,a C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group; oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Thehalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, andC₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on In^(A)and/or In^(B) in formula (I) can be any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (I)). Asubstituent on In^(A) and/or In^(B) independently can be, in certainaspects, a C₁ to C₃₆ halogenated hydrocarbyl group, where thehalogenated hydrocarbyl group indicates the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thehydrocarbyl group. The halogenated hydrocarbyl group often can be ahalogenated alkyl group, a halogenated alkenyl group, a halogenatedcycloalkyl group, a halogenated aryl group, or a halogenated aralkylgroup. Representative and non-limiting halogenated hydrocarbyl groupsinclude pentafluorophenyl, trifluoromethyl (CF₃), and the like.

As a non-limiting example, each substituent on In^(A) and/or In^(B)independently can be H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group (or other substituted aryl group),a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group; alternatively, H; alternatively,Cl; alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group;alternatively, an allyldimethylsilyl group; or alternatively, a1-methylcyclohexyl group.

In one aspect, for example, each substituent on In^(A) and/or In^(B)independently can be H or a C₁ to C₁₈ hydrocarbyl group; alternatively,a C₁ to C₁₀ hydrocarbyl group; alternatively, a C₁ to C₆ linear orbranched alkyl group (e.g., a tert-butyl group); alternatively, H, Cl,CF₃, a methyl group, an ethyl group, a propyl group, a butyl group(e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group, and the like; alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, a decenyl group, a phenyl group, a tolyl group, or abenzyl group; alternatively, a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, or a hexyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, a propylgroup; alternatively, a butyl group; or alternatively, a tert-butylgroup.

In formula (I), each R independently can be H, a C₁ to C₃₆ hydrocarbylgroup, or a C₁ to C₃₆ hydrocarbylsilyl group. The C₁ to C₃₆ hydrocarbylgroup and C₁ to C₃₆ hydrocarbylsilyl group which can be a R in formula(I) can be any C₁ to C₃₆ hydrocarbyl group or C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (I)). It iscontemplated that each R can be either the same or a differentsubstituent group. For example, each R independently can be H, a C₁ toC₁₈ hydrocarbyl group, or a C₁ to C₁₈ hydrocarbylsilyl group. In someaspects, each R independently can be a C₁ to C₆ linear or branched alkylgroup (e.g., an isopropyl group). In other aspects, each R independentlycan be a methyl group, an ethyl group, a propyl group, a butyl group, apentyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group, a phenyl group, a tolyl group, a benzyl group, anaphthyl group, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group, and the like.

An illustrative and non-limiting example of a boron-bridged,indenyl-indenyl metallocene compound with an alkenyl substituent caninclude the following compound:

Methods of making boron-bridged metallocene complexes of the presentinvention also are encompassed herein. These metallocene complexes canbe synthesized by various suitable procedures, such as those describedin WO 00/20462, the disclosure of which is incorporated herein byreference in its entirety, and the procedures provided herein. Arepresentative synthesis scheme is provided below, where theboron-bridged metallocene compound is synthesized in a multistepprocess.

Also encompassed herein are ligand compounds which can be used to formmetallocene compounds having formula (I). Such ligand compounds can havethe formula:

The selections for In^(A), In^(B), and each R in formula (A) are thesame as those described herein for formula (I). Hence, in formula (A),In^(A) can be an indenyl group with an alkenyl substituent, and In^(B)can be an indenyl group that does not contain any substituents; orIn^(A) can be an indenyl group with an alkenyl substituent, and In^(B)can be an indenyl group that contains one or more substituents. Each Rindependently can be H, or any C₁ to C₃₆ hydrocarbyl group or C₁ to C₃₆hydrocarbylsilyl group disclosed herein.

Illustrative and non-limiting examples of indenyl-indenyl boron-bridgedligand compounds (with the alkenyl on an indenyl group) can include thefollowing compounds:

and the like.

Using analogous synthesis schemes to those provided herein, ligand andmetallocene complexes with substituents on the nitrogen other thanisopropyl can be derived, and complexes with indenyl groups with variousalkenyl substituents (and optionally, other substituents) can bederived. Moreover, using analogous synthesis schemes to those providedherein, metallocene complexes with monoanionic ligands other than Cl(e.g., hydrocarbyl, hydrocarbylaminyl, hydrocarbylsilyl, etc.) can bederived, and complexes with various transition metals can be derived.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator-support. In one aspect, the activator-supportcan comprise a solid oxide treated with an electron-withdrawing anion.Alternatively, in another aspect, the activator-support can comprise asolid oxide treated with an electron-withdrawing anion, the solid oxidecontaining a Lewis-acidic metal ion. Non-limiting examples of suitableactivator-supports are disclosed in, for instance, U.S. Pat. Nos.7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, and 8,703,886,which are incorporated herein by reference in their entirety.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form an activator-support, eithersingly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, and the like. The solid oxideused herein also can encompass oxide materials such as silica-coatedalumina, as described in U.S. Pat. No. 7,884,163.

Accordingly, in one aspect, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, silica-titania,zirconia, silica-zirconia, magnesia, boria, zinc oxide, any mixed oxidethereof, or any combination thereof. In another aspect, the solid oxidecan comprise alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania,silica-titania, zirconia, silica-zirconia, magnesia, boria, or zincoxide, as well as any mixed oxide thereof, or any mixture thereof. Inanother aspect, the solid oxide can comprise silica, alumina, titania,zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or anycombination thereof. In yet another aspect, the solid oxide can comprisesilica-alumina, silica-coated alumina, silica-titania, silica-zirconia,alumina-boria, or any combination thereof. In still another aspect, thesolid oxide can comprise alumina, silica-alumina, silica-coated alumina,or any mixture thereof; alternatively, alumina; alternatively,silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have an silica content from about 5 to about 95% byweight. In one aspect, the silica content of these solid oxides can befrom about 10 to about 80%, or from about 20% to about 70%, silica byweight. In another aspect, such materials can have silica contentsranging from about 15% to about 60%, or from about 25% to about 50%,silica by weight. The solid oxides contemplated herein can have anysuitable surface area, pore volume, and particle size, as would berecognized by those of skill in the art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspect,the electron-withdrawing component can be an electron-withdrawing anionderived from a salt, an acid, or other compound, such as a volatileorganic compound, that serves as a source or precursor for that anion.Examples of electron-withdrawing anions can include, but are not limitedto, sulfate, bisulfate, fluoride, chloride, bromide, iodide,fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, tungstate, molybdate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsalso can be employed. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, and the like, or any combinationthereof, in some aspects provided herein. In other aspects, theelectron-withdrawing anion can comprise sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof. Yet, in otheraspects, the electron-withdrawing anion can comprise fluoride and/orsulfate.

The activator-support generally can contain from about 1 to about 25 wt.% of the electron-withdrawing anion, based on the weight of theactivator-support. In particular aspects provided herein, theactivator-support can contain from about 1 to about 20 wt. %, from about2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 toabout 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12wt. %, or from about 4 to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the activator-support.

In an aspect, the activator-support can comprise fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,as well as any mixture or combination thereof. In another aspect, theactivator-support employed in the catalyst systems described herein canbe, or can comprise, a fluorided solid oxide and/or a sulfated solidoxide, non-limiting examples of which can include fluorided alumina,sulfated alumina, fluorided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, fluorided silica-coated alumina, sulfatedsilica-coated alumina, and the like, as well as combinations thereof. Inyet another aspect, the activator-support can comprise fluoridedalumina; alternatively, chlorided alumina; alternatively, sulfatedalumina; alternatively, fluorided silica-alumina; alternatively,sulfated silica-alumina; alternatively, fluorided silica-zirconia;alternatively, chlorided silica-zirconia; alternatively, sulfatedsilica-coated alumina; or alternatively, fluorided silica-coatedalumina.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metal ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, etc.) are wellknown to those of skill in the art.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, andthis includes any combinations of these materials. In one aspect, theco-catalyst can comprise an organoaluminum compound. In another aspect,the co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof. In yet another aspect, the co-catalyst can comprisean aluminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions of thisinvention are not limited to the co-catalysts described above. Othersuitable co-catalysts are well known to those of skill in the artincluding, for example, those disclosed in U.S. Pat. Nos. 3,242,099,4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,5997,601,665, 7,884,163, 8,114,946, and 8,309,485, which are incorporatedherein by reference in their entirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some aspects, the present invention employs catalyst compositionscontaining a boron-bridged, indenyl-indenyl metallocene compound and anactivator (one or more than one). These catalyst compositions can beutilized to produce polyolefins—homopolymers, copolymers, and thelike—for a variety of end-use applications. Boron-bridged metallocenecompounds are discussed hereinabove. In aspects of the presentinvention, it is contemplated that the catalyst composition can containmore than one boron-bridged metallocene compound. Further, additionalcatalytic compounds—other than those specified as a boron-bridgedmetallocene compound—can be employed in the catalyst compositions and/orthe polymerization processes, provided that the additional catalyticcompound does not detract from the advantages disclosed herein.Additionally, more than one activator also may be utilized.

Generally, catalyst compositions of the present invention comprise aboron-bridged metallocene compound having formula (I) and an activator.In aspects of the invention, the activator can comprise anactivator-support (e.g., an activator-support comprising a solid oxidetreated with an electron-withdrawing anion). Activator-supports usefulin the present invention are disclosed herein. Optionally, such catalystcompositions can further comprise one or more than one co-catalystcompound or compounds (suitable co-catalysts, such as organoaluminumcompounds, also are discussed herein). Thus, a catalyst composition ofthis invention can comprise a boron-bridged metallocene compound, anactivator-support, and an organoaluminum compound. For instance, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof or alternatively, afluorided solid oxide and/or a sulfated solid oxide. Additionally, theorganoaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof. Accordingly, a catalyst composition consistent with aspects ofthe invention can comprise (or consist essentially of, or consist of) aboron-bridged metallocene compound; sulfated alumina (or fluoridedsilica-alumina, or fluorided silica-coated alumina); andtriethylaluminum (or triisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises a boron-bridged metallocene compound, anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and/or other similarmaterials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention can consistessentially a boron-bridged metallocene compound, an activator-support,and an organoaluminum compound, wherein no other materials are presentin the catalyst composition which would increase/decrease the activityof the catalyst composition by more than about 10% from the catalystactivity of the catalyst composition in the absence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising a boron-bridged metallocene compound and anactivator-support can further comprise an optional co-catalyst. Suitableco-catalysts in this aspect can include, but are not limited to,aluminoxane compounds, organoboron or organoborate compounds, ionizingionic compounds, organoaluminum compounds, organozinc compounds,organomagnesium compounds, organolithium compounds, and the like, or anycombination thereof or alternatively, organoaluminum compounds,organozinc compounds, organomagnesium compounds, organolithiumcompounds, or any combination thereof. More than one co-catalyst can bepresent in the catalyst composition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprise aboron-bridged metallocene compound and an activator, wherein theactivator can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof alternatively, an aluminoxane compound; alternatively, anorganoboron or organoborate compound; or alternatively, an ionizingionic compound.

In a particular aspect contemplated herein, the catalyst composition isa catalyst composition comprising an activator (one or more than one)and only one boron-bridged metallocene compound having formula (I). Inthese and other aspects, the catalyst composition can comprise anactivator (e.g., an activator-support comprising a solid oxide treatedwith an electron-withdrawing anion), only one boron-bridged metallocenecompound, and a co-catalyst (one or more than one), such as anorganoaluminum compound.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence. In one aspect, the catalystcomposition can be produced by a process comprising contacting themetallocene compound and the activator, while in another aspect, thecatalyst composition can be produced by a process comprising contacting,in any order, the metallocene compound, the activator, and theco-catalyst.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support are employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocenecompound to activator-support can be in a range from about 1:1 to about1:1,000,000. If more than one metallocene compound and/or more thanactivator-support is/are employed, this ratio is based on the totalweights of the respective components. In another aspect, this weightratio can be in a range from about 1:5 to about 1:100,000, or from about1:10 to about 1:10,000. Yet, in another aspect, the weight ratio of themetallocene compound to the activator-support can be in a range fromabout 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 50,000 grams, greater than about 75,000grams, greater than 100,000 grams, greater than about 125,000 grams,etc., of ethylene polymer (homopolymer or copolymer, as the contextrequires) per gram of the boron-bridged metallocene compound per hour(abbreviated g/g/h). In another aspect, the catalyst activity can begreater than about 150,000, greater than about 175,000, or greater thanabout 200,000 g/g/h. In still another aspect, catalyst compositions ofthis invention can be characterized by having a catalyst activitygreater than about 250,000, greater than about 300,000, or greater thanabout 350,000 g/g/h, and often can range up to 1,000,000-2,000,000g/g/h. These activities are measured under slurry polymerizationconditions, with a triisobutylaluminum co-catalyst, using isobutane asthe diluent, at a polymerization temperature of 80° C. and a reactorpressure of 400 psig. Additionally, in some aspects, the activator cancomprise an activator-support, such as sulfated alumina, fluoridedsilica-alumina, or fluorided silica-coated alumina, although not limitedthereto.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise a boron-bridged metallocene compound,an activator, and an optional co-catalyst. Suitable boron-bridgedmetallocene compounds, activators, and co-catalysts are discussedherein.

In accordance with one aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a boron-bridgedmetallocene compound having formula (I) and an activator, wherein theactivator comprises an activator-support. The catalyst composition,optionally, can further comprise one or more than one organoaluminumcompound or compounds (or other suitable co-catalyst). Thus, a processfor polymerizing olefins in the presence of a catalyst composition canemploy a catalyst composition comprising a boron-bridged metallocenecompound, an activator-support, and an organoaluminum compound. In someaspects, the activator-support can comprise (or consist essentially of,or consist of) fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, and the like, or combinations thereof oralternatively, a fluorided solid oxide and/or a sulfated solid oxide. Insome aspects, the organoaluminum compound can comprise (or consistessentially of, or consist of) trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a boron-bridgedmetallocene, an activator-support, and an optional co-catalyst, whereinthe co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organoaluminumcompound, an organozinc compound, an organomagnesium compound, or anorganolithium compound, or any combination thereof. Hence, aspects ofthis invention are directed to a process for polymerizing olefins in thepresence of a catalyst composition, the process comprising contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) under polymerization conditions to produce anolefin polymer, and the catalyst composition can comprise aboron-bridged metallocene compound, an activator-support, and analuminoxane compound; alternatively, a boron-bridged metallocenecompound, an activator-support, and an organoboron or organoboratecompound; alternatively, a boron-bridged metallocene compound, anactivator-support, and an ionizing ionic compound; alternatively, aboron-bridged metallocene compound, an activator-support, and anorganoaluminum compound; alternatively, a boron-bridged metallocenecompound, an activator-support, and an organozinc compound;alternatively, a boron-bridged metallocene compound, anactivator-support, and an organomagnesium compound; or alternatively, aboron-bridged metallocene compound, an activator-support, and anorganolithium compound. Furthermore, more than one co-catalyst can beemployed, e.g., an organoaluminum compound and an aluminoxane compound,an organoaluminum compound and an ionizing ionic compound, etc.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising only oneboron-bridged metallocene compound, an activator-support, and anorganoaluminum compound.

In accordance with yet another aspect of the invention, thepolymerization process can employ a catalyst composition comprising aboron-bridged metallocene compound and an activator, wherein theactivator comprises an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof; alternatively, an aluminoxane compound; alternatively, anorganoboron or organoborate compound; or alternatively, an ionizingionic compound.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a loop reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and, optionally, an olefin comonomer under polymerizationconditions to produce an olefin polymer. The olefin polymer (e.g.,ethylene homopolymer, ethylene copolymer, etc.) produced by the processcan have any of the polymer properties disclosed herein, for example, adensity from about from about 0.87 to about 0.96, from about 0.87 toabout 0.94, from about 0.88 to about 0.93, from about 0.89 to about0.93, from about 0.895 to about 0.925, from about 0.90 to about 0.92g/cm³, etc., and/or less than about 0.01 long chain branches (LCB) per1000 total carbon atoms, e.g., less than about 0.008 LCB per 1000 totalcarbon atoms, less than about 0.005 LCB per 1000 total carbon atoms,less than about 0.003 LCB per 1000 total carbon atoms, etc., and/or aratio of Mw/Mn in any range disclosed herein, e.g., from about 2 toabout 6, from about 2 to about 5, from about 3 to about 6, from about 3to about 5, etc., and/or a conventional comonomer distribution, and/or aunimodal molecular weight distribution. The disclosed catalyst systemsand polymerization processes are capable of producing unique ethylenecopolymers, such as ethylene copolymers characterized by a melt index ina range from about 25 to about 2000 g/10 min (or from about 50 to about2000 g/10 min, or from about 50 to about 1000 g/10 min), and a densityin a range from about 0.87 to about 0.92 g/cm³ (or from about 0.88 toabout 0.92 g/cm³, or from about 0.88 to about 0.915 g/cm³).

Unexpectedly, the catalyst systems and polymerization processes of thisinvention, employing a boron bridged metallocene compound having formula(I), can have very good comonomer incorporation, as illustrated by arelatively large drop in density based on the increase in thecomonomer:monomer molar ratio. For instance, an ethylene copolymer(e.g., an ethylene/1-hexene copolymer) can have a decrease indensity—based on an increase in comonomer:monomer molar ratio (e.g.,1-hexene:ethylene molar ratio) from 0.6:1 to 1.2:1—of at least about0.005 g/cm³ (and often up to about 0.03 g/cm³); alternatively, adecrease of at least about 0.01 g/cm³; alternatively, a decrease of atleast about 0.015 g/cm³; or alternatively, a decrease of at least about0.02 g/cm³.

In aspects of this invention, and surprisingly, very low densityethylene copolymers can be produced in a polymerization reactor systemcomprises a loop slurry reactor, and moreover, such copolymers can beproduced without reactor fouling. For instance, there can be no foulingobserved in the loop slurry reactor at an olefin copolymer density ofless than about 0.918; alternatively, less than about 0.91;alternatively, less than about 0.905; alternatively, less than about0.90; alternatively, less than about 0.895; or alternatively, less thanabout 0.89 g/cm³. In some aspects, there can be no fouling observed whenthe olefin copolymer density is greater than about 0.88 g/cm³.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise a boron-bridged metallocene, an activator, andan optional co-catalyst, and wherein the polymerization process isconducted in the absence of added hydrogen (no hydrogen is added to thepolymerization reactor system). As one of ordinary skill in the artwould recognize, hydrogen can be generated in-situ by metallocenecatalyst compositions in various olefin polymerization processes, andthe amount generated can vary depending upon the specific catalystcomposition and metallocene compound employed, the type ofpolymerization process used, the polymerization reaction conditionsutilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises a boron-bridged metallocene, anactivator, and an optional co-catalyst, and wherein the polymerizationprocess is conducted in the presence of added hydrogen (hydrogen isadded to the polymerization reactor system). For example, the ratio ofhydrogen to the olefin monomer in the polymerization process can becontrolled, often by the feed ratio of hydrogen to the olefin monomerentering the reactor. The added hydrogen to olefin monomer ratio in theprocess can be controlled at a weight ratio which falls within a rangefrom about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, orfrom about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymers (e.g.,ethylene/α-olefin copolymers, ethylene homopolymers, etc.) produced byany of the polymerization processes disclosed herein. Articles ofmanufacture can be formed from, and/or can comprise, the polymersproduced in accordance with this invention.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and comonomer(s) described herein. For example, theolefin polymer can comprise an ethylene homopolymer, a propylenehomopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/l-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/l-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

In particular aspects, and unexpectedly, the ethylene copolymersdisclosed herein often can have a unique combination of a high meltindex and a low density. Moreover, such copolymers can be produced in anolefin polymerization process in which no hydrogen is added. Anillustrative and non-limiting example of an ethylene/α-olefin copolymer(e.g., an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer,an ethylene/l-octene copolymer) consistent with aspects of thisinvention can have a melt index (MI) greater than or equal to about 25g/10 min, and a density less than or equal to about 0.92 g/cm³. Suitablenon-limiting ranges for the MI of the ethylene copolymer can include aMI greater than or equal to about 35, a MI greater than or equal toabout 50, a MI greater than or equal to about 75, a MI greater than orequal to about 100, a MI in a range from about 25 to about 2000, a MI ina range from about 25 to about 1000, a MI in a range from about 50 toabout 2000, a MI in a range from about 50 to about 1500, a MI in rangefrom about 50 to about 1000, a MI in a range from about 50 to about 750,a MI in a range from about 35 to about 1500, a MI in a range from about100 to about 1500, a MI in a range from about 75 to about 750, or a MIin a range from about 35 to about 250 g/10 min, and the like. Suitablenon-limiting ranges for the density of the ethylene copolymer caninclude a density less than or equal to about 0.918, a density less thanor equal to about 0.915, a density less than or equal to about 0.91, adensity less than or equal to about 0.908, a density in a range fromabout 0.87 to about 0.92, a density in a range from about 0.87 to about0.918, a density in a range from about 0.87 to about 0.91, a density ina range from about 0.88 to about 0.92, a density in a range from about0.88 to about 0.918, a density in a range from about 0.88 to about0.915, a density in a range from about 0.88 to about 0.91, or a densityin a range from about 0.875 to about 0.92 g/cm³, and the like.Accordingly, another illustrative and non-limiting example of anethylene copolymer of the present invention can have a melt index in arange from about 25 to about 2000 g/10 min (or from about 50 to about2000 g/10 min, or from about 50 to about 1000 g/10 min), and a densityin a range from about 0.87 to about 0.92 g/cm³ (or from about 0.88 toabout 0.92 g/cm³, or from about 0.88 to about 0.915 g/cm³). Theseillustrative and non-limiting examples of ethylene copolymers consistentwith the present invention also can have any of the copolymer propertieslisted below and in any combination.

The ethylene copolymer, in some aspects, can have a unimodal molecularweight distribution. Additionally or alternatively, the ethylenecopolymer can have very low levels of long chain branching, withtypically less than about 0.01 long chain branches (LCB) per 1000 totalcarbon atoms, such as, for instance, less than about 0.008 LCB, lessthan about 0.005 LCB, or less than about 0.003 LCB, per 1000 totalcarbon atoms.

The ethylene copolymer, in some aspects, can have a narrow molecularweight distribution. For instance, the ethylene copolymer can have aratio of Mw/Mn of less than or equal to about 6, such as in a range fromabout 2 to about 6, from about 2 to about 5, from about 3 to about 6, orfrom about 3 to about 5. The ethylene copolymer, in some aspects, canhave a weight-average molecular weight (Mw) in a range from about 16,000to about 60,000, from about 20,000 to about 55,000, or from about 18,000to about 50,000 g/mol. The Mw of the ethylene copolymer can be in arange from about 20,000 to about 50,000, from about 20,000 to about45,000, or from about 25,000 to about 40,000 g/mol, in further aspectsof this invention. Additionally or alternatively, the ethylene copolymercan have a number-average molecular weight (Mn) in a range from about3,000 to about 20,000, from about 3,000 to about 18,000, or from about4,000 to about 16,000 g/mol. The Mn of the ethylene copolymer can be ina range from about 4,000 to about 18,000, from about 4,000 to about15,000, or from about 3,500 to about 13,500 g/mol, in further aspects ofthis invention.

Ethylene copolymers, for example, produced using the polymerizationprocesses and catalyst systems described hereinabove can, in someaspects, have a conventional comonomer distribution; generally, thehigher molecular weight components of the polymer have less comonomerincorporation than the lower molecular weight components. Typically,there is decreasing comonomer incorporation with increasing molecularweight. In one aspect, the number of short chain branches (SCB) per 1000total carbon atoms of the polymer can be greater at Mn than at Mw. Inanother aspect, the number of SCB per 1000 total carbon atoms of thepolymer can be greater at Mn than at Mz. In yet another aspect, thenumber of SCB per 1000 total carbon atoms of the polymer can be greaterat Mw than at Mz.

In addition to the above-described ethylene copolymers, other olefinpolymers (e.g., higher density ethylene copolymers, ethylenehomopolymers, etc.) can be produced using the catalyst systems andpolymerization processes described herein. The densities ofethylene-based polymers produced using the catalyst systems andpolymerization processes described herein often range from about 0.87 toabout 0.96 g/cm³. In one aspect of this invention, the density of theethylene polymer can be in a range from about 0.87 to about 0.94 g/cm³.Yet, in another aspect, the density can be in a range from about 0.88 toabout 0.93 g/cm³, such as, for example, from about 0.89 to about 0.93g/cm³, from about 0.895 to about 0.925 g/cm³, or from about 0.90 toabout 0.92 g/cm³.

Olefin polymers (e.g., ethylene homopolymers and ethylene copolymers)produced using the catalyst systems and polymerization processesdescribed herein generally can have a ratio of Mw/Mn in a range fromabout 2 to about 6. In some aspects disclosed herein, the ratio of Mw/Mncan be in a range from about 2 to about 5, from about 3 to about 6, orfrom about 3 to about 5. Additionally or alternatively, the olefinpolymer, in further aspects, can have a ratio of Mz/Mw in a range fromabout 1.5 to about 3, from about 1.5 to about 2.5, from about 1.8 toabout 2.3, from about 2 to about 2.5, or from about 2 to about 2.2.Additionally or alternatively, the olefin polymer, in some aspects, canhave a weight-average molecular weight (Mw) in a range from about 16,000to about 60,000, from about 20,000 to about 55,000, or from about 18,000to about 50,000 g/mol. The Mw can be in a range from about 20,000 toabout 50,000, from about 20,000 to about 45,000, or from about 25,000 toabout 40,000 g/mol, in further aspects of this invention. Additionallyor alternatively, the olefin polymer can have a number-average molecularweight (Mn) in a range from about 3,000 to about 20,000, from about3,000 to about 18,000, or from about 4,000 to about 16,000 g/mol. The Mncan be in a range from about 4,000 to about 18,000, from about 4,000 toabout 15,000, or from about 3,500 to about 13,500 g/mol, in furtheraspects of this invention. Additionally or alternatively, the olefinpolymer can have a unimodal molecular weight distribution.

Generally, olefin polymers produced using the catalyst systems andpolymerization processes described herein can have low levels of longchain branching, with typically less than about 0.01 long chain branches(LCB) per 1000 total carbon atoms, and more often, less than about 0.008LCB per 1000 total carbon atoms. In some aspects, the number of LCB per1000 total carbon atoms can be less than about 0.005, less than about0.003 LCB per 1000 total carbon atoms, or less than about 0.002 LCB per1000 total carbon atoms.

Olefin polymers, for example, produced using the catalyst systems andpolymerization processes described herein can, in some aspects, have aconventional comonomer distribution, generally, the lower molecularweight components of the polymer have higher comonomer incorporationthan the higher molecular weight components. Typically, there isdecreasing comonomer incorporation with increasing molecular weight. Inone aspect, the number of short chain branches (SCB) per 1000 totalcarbon atoms of the polymer can be greater at Mn than at Mw. In anotheraspect, the number of SCB per 1000 total carbon atoms of the polymer canbe greater at Mn than at Mz.

Polymers of ethylene, whether homopolymers, copolymers, and so forth,can be formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise a boron-bridged metallocene (e.g.,having formula (I)), an activator (e.g., an activator-support comprisinga solid oxide treated with an electron-withdrawing anion), and anoptional co-catalyst (e.g., an organoaluminum compound); and (ii)forming an article of manufacture comprising the olefin polymer. Theforming step can comprise blending, melt processing, extruding, molding(e.g., blow molding), or thermoforming, and the like, includingcombinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight. Polymer density was determined in grams per cubiccentimeter (g/cm³) on a compression molded sample, cooled at about 15°C. per hour, and conditioned for about 40 hours at room temperature inaccordance with ASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 200 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mpis the peak molecular weight, Mn is the number-average molecular weight,Mw is the weight-average molecular weight, and Mz is the z-averagemolecular weight.

The long chain branches (LCB) per 1000 total carbon atoms can becalculated using the method of Janzen and Colby (J. Mol. Struct.,485/486, 569-584 (1999)), from values of zero shear viscosity, η_(o)(determined from the Carreau-Yasuda model), and measured values of Mwobtained using a Dawn EOS multiangle light scattering detector (Wyatt).See also U.S. Pat. No. 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y.Yu, D. C. Rohlfing, G. R Hawley, and P. J. DesLauriers, PolymerPreprint, 44, 50, (2003). These references are incorporated herein byreference in their entirety.

Short chain branch (SCB) content and short chain branching distribution(SCBD) across the molecular weight distribution can be determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system is a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IRS MCT detector (IRS) (Polymer Char, Spain) isconnected to the GPC columns via a hot-transfer line. Chromatographicdata are obtained from two output ports of the IRS detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions are set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIRS detector sample cell are set at 150° C., while the temperature ofthe electronics of the IRS detector is set at 60° C. Short chainbranching content is determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve is a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) is used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution areobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume isconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Fluorided silica-coated alumina activator-supports were prepared asfollows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g, apore volume of about 1.3 mL/g, and an average particle size of about 100microns. The alumina was first calcined in dry air at about 600° C. forapproximately 6 hours, cooled to ambient temperature, and then contactedwith tetraethylorthosilicate in isopropanol to equal 25 wt. % SiO₂.After drying, the silica-coated alumina was calcined at 600° C. for 3hours. Fluorided silica-coated alumina (7 wt. % F) was prepared byimpregnating the calcined silica-coated alumina with an ammoniumbifluoride solution in methanol, drying, and then calcining for 3 hoursat 600° C. in dry air. Afterward, the fluorided silica-coated aluminawas collected and stored under dry nitrogen, and was used withoutexposure to the atmosphere.

Example 1

Metallocene MET-1, shown below, was synthesized by first reactinglithiated indene with 5-bromo-1-pentene. Pure 3-(1-pentenyl) indene wasobtained via vacuum distillation as a pale yellow oil. One mole of3-(1-pentenyl) indene was added to diethyl ether and cooled to −74° C.,and one mole of n-butyllithium was added. The reaction mixture wasstirred at 21° C. for 3 hr, then cooled again to −74° C., followed bythe addition of a diethyl ether solution ofdichloro(diisopropylamino)boron, and then stirred for 12 hr whilewarming to 21° C. The resulting yellow slurry was centrifuged, and thebright yellow solution was poured off and solvent removed under reducedpressure. Monochloro(diisopropylamino)-3-(1-pentenyl)indenylboron wasobtained as a yellow oil. 1 mol of indene was added to diethyl ether andcooled to −74° C., then n-butyllithium was added and the solution wasstirred at 20° C. for 3 hr. The solution was cooled to −74° C. and adiethyl ether solution ofmonochloro(diisopropylamino)-3-(1-pentenyl)indenylboron was added,resulting in an orange slurry, which was stirred at 20° C. for 12 hr.The reaction solution was filtered into a Schlenk-tube and the solventwas removed under reduced pressure, yielding Ligand-1 shown below.

A portion of the ligand product was mixed with diethyl ether and cooledto −34° C., then 2 moles of n-butyllithium was added and the solutionwas stirred at 20° C. for 3 hr. A suspension of ZrCl₄ in diethyl etherwas cooled to −34° C., followed by addition of the ligand mixture; thesolution turned to a red slurry. After stirring for 12 hr at 21° C., thesolution was centrifuged, removed, and concentrated to a dark redresidue. The solid was extracted with pentane, filtered, andconcentrated to yield a red solid product of MET-1 {mixture of rac/mesoisomers—¹H NMR (300 MHz, C₆D₆): δ 7.26-7.34 (2H, m), 7.12-7.20 (2H, m),6.94-7.03 (2H, m), 6.69-6.77 (2H, m), 5.69-5.80 (2H, m), 5.405 (1H, d),5.22 (1H, s), 5.01 (1H, d), 4.97 (1H, d), 3.758-3.935 (2.76H, m),2.95-3.08 (2.35H, m), 2.80-2.94 (2.55H, m), 2.02 (3.40H, m), 1.55-1.71(3.77H, m), 1.07-1.26 (13.54H, m) ppm}.

Example 2

Using a synthesis procedure analogous to that of Example 1, thefollowing bis-indenyl ligand compound was produced:

Examples 3-7

Examples 3-7 were produced using the following polymerization procedure.All polymerization runs were conducted in a one-gallon stainless steelreactor. Isobutane (1.2 L) was used in all runs. A metallocene solutionof MET-1 was prepared at about 1 mg/mL in toluene. Approximately 100 mgof fluorided silica-coated alumina, 0.8 mmol of alkyl aluminum(triisobutylaluminum), and the metallocene solution (containing0.35-0.45 mg of MET-1) were added in that order through a charge portwhile slowly venting isobutane vapor. The charge port was closed andisobutane was added. The contents of the reactor were stirred and heatedto the desired run temperature of about 80° C., and ethylene and1-hexene were then introduced into the reactor. No hydrogen was added.Ethylene was fed on demand to maintain the target pressure of about 400psig pressure for 60 min. The reactor was maintained at the desiredtemperature throughout the run by an automated heating-cooling system.

Table I summarizes certain polymerization conditions and catalystactivities for Examples 3-7, as well as the respective melt index, highload melt index, and density for the resulting polymers of Examples 3-7.The catalyst activities ranged from 100,000 grams to over 600,000 gramsof polymer per gram of MET-1 per hour, and ranged from 1000 grams toover 6000 grams of polymer per gram of the activator-support per hour.As shown in Table I, the melt index and high load melt index increaseddramatically, and the density decreased dramatically, with the additionof 1-hexene comonomer. Surprisingly, no reactor fouling was observed forany of Examples 3-7.

FIG. 1 illustrates the molecular weight distributions (amount of polymerversus logarithm of molecular weight) for the ethylene copolymers ofExamples 3-7, while Table II summarizes specific molecular weightparameters for the copolymers of Examples 3-7. Polymer molecular weightsdecreased with the addition of 1-hexene comonomer.

FIG. 2 illustrates the molecular weight distributions and short chainbranch distributions of the polymers of Examples 3-7. In addition torelatively narrow molecular weight distributions, the polymers ofExamples 3-7 exhibited a conventional (decreasing) comonomerdistribution (e.g., there are relatively more short chain branches (SCB)at the lower molecular weights, e.g., the number of SCB per 1000 totalcarbon (TC) atoms of the polymer at Mz (or Mw) is less than at Mn).

Table III summarizes the density and 1-hexene comonomer levels in thecopolymers of Examples 3-7. Unexpectedly, catalyst systems containingMET-1 provided good comonomer incorporation, as indicated by a largedrop in density based on the increase in the comonomer:monomer molarratio. For instance, Example 5 (100 g 1-hexene) reflects an approximate0.6:1 molar ratio of 1-hexene:ethylene, while Example 6 reflects anapproximate 1.2:1 molar ratio of 1-hexene:ethylene molar ratio. Thedecrease in density, based on the increase in the 1-hexene:ethylenemolar ratio from 0.6:1 to 1.2:1, was 0.0227 g/cm³.

TABLE I Examples 3-7. MET-1 1-hexene Polymer Metallocene Supportmetallocene comonomer produced activity activity MI HLMI Density Example(mg) (g) (g) (g/g/hr) (g/g/hr) (g/10 min) (g/10 min) (g/cc) 3 0.40 50246 615,000 6150 28.5 313 0.9307 4 0.37 75 60 162,000 1500 61.2 3900.9188 5 0.44 100 184 418,000 4600 123 2218 0.9078 6 0.35 200 91 261,0002280 530 Too High 0.8851 7 0.40 350 40 100,000 1000 Too High Too High<0.88

TABLE II Examples 3-7-Molecular weight parameters. 1-hexene Mn/1000Mw/1000 Mz/1000 Mp/1000 Example (g) (g/mol) (g/mol) (g/mol) (g/mol)Mw/Mn Mz/Mw 3 50 14.2 52.1 110.1 48.7 3.67 2.11 4 75 12.8 42.7 89.6 36.93.35 2.10 5 100 8.8 36.2 74.7 31.4 4.13 2.06 6 200 7.1 27.9 56.3 25.03.95 2.02 7 350 4.6 23.3 53.0 19.1 5.09 2.27

TABLE III Examples 3-7-Density and 1-hexene content in the polymer.Ethyl- 1-hexene Density 1-hexene Ethylene 1-hexene ene Example (g)(g/cc) (mol %) (mol %) (wt. %) (wt. %) 3 50 0.9307 1.2 98.8 3.3 96.7 475 0.9188 3.0 97.0 8.1 91.9 5 100 0.9078 3.4 96.6 9.2 90.8 6 200 0.88515.9 94.1 14.6 85.4 7 350 <0.88 7.0 93.0 17.0 83.0

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1

A ligand compound having the formula:

wherein:In^(A) is an indenyl group with an alkenyl substituent; In^(B) is anindenyl group, optionally substituted with any substituent (one or more)disclosed herein; and each R independently is H, a C₁ to C₃₆ hydrocarbylgroup, or a C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 2

A metallocene compound having the formula:

wherein:M is Ti, Zr, or Hf; each X independently is a monoanionic ligand; In^(A)is an indenyl group with an alkenyl substituent; In^(B) is an indenylgroup, optionally substituted with any substituent (one or more)disclosed herein; and each R independently is H, a C₁ to C₃₆ hydrocarbylgroup, or a C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 3

The compound defined in embodiment 1 or 2, wherein In^(B) does not havean alkenyl substituent.

Embodiment 4

The compound defined in any one of embodiments 1-3, wherein In^(A) hasone substituent in addition to the alkenyl substituent.

Embodiment 5

The compound defined in any one of embodiments 1-4, wherein the alkenylsubstituent is any alkenyl group disclosed herein, e.g., a C₂ to C₁₈alkenyl group, a C₃ to C₁₂ linear alkenyl group, a C₃ to C₈ terminalalkenyl group, etc.

Embodiment 6

The compound defined in any one of embodiments 1-4, wherein the alkenylsubstituent is an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, or a decenyl group.

Embodiment 7

The compound defined in any one of embodiments 1-4, wherein the alkenylsubstituent is a C₃ to C₁₂ linear alkenyl group.

Embodiment 8

The compound defined in any one of embodiments 1-4, wherein the alkenylsubstituent is a C₃ to C₈ terminal alkenyl group (e.g., a C₃ to C₆terminal alkenyl group).

Embodiment 9

The compound defined in any one of embodiments 1-8, wherein In^(A) has asubstituent (one or more) in addition to the alkenyl substituent, e.g.,H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group.

Embodiment 10

The compound defined in any one of embodiments 1-9, wherein In^(B) has asubstituent (one or more), e.g., H, a halide, a C₁ to C₃₆ hydrocarbylgroup, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 11

The compound defined in embodiment 9 or 10, wherein the substituent (oreach substituent independently) is H or a C₁ to C₁₈ hydrocarbyl group.

Embodiment 12

The compound defined in embodiment 9 or 10, wherein the substituent (oreach substituent independently) is H, Cl, CF₃, a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group, a benzyl group, a naphthyl group,a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilylgroup, an allyldimethylsilyl group, or a 1-methylcyclohexyl group.

Embodiment 13

The compound defined in embodiment 9 or 10, wherein the substituent (oreach substituent independently) is a C₁ to C₆ linear or branched alkylgroup (e.g., a tert-butyl group).

Embodiment 14

The compound defined in any one of embodiments 1-13, wherein each Rindependently is H or any C₁ to C₁₈ hydrocarbyl group or C₁ to C₁₈hydrocarbylsilyl group disclosed herein.

Embodiment 15

The compound defined in any one of embodiments 1-13, wherein each Rindependently is a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group, a phenyl group, a tolyl group, a benzylgroup, a naphthyl group, a trimethylsilyl group, a triisopropylsilylgroup, a triphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group.

Embodiment 16

The compound defined in any one of embodiments 1-13, wherein each Rindependently is a C₁ to C₆ linear or branched alkyl group (e.g., anisopropyl group).

Embodiment 17

The compound defined in any one of embodiments 2-16, wherein M is Ti.

Embodiment 18

The compound defined in any one of embodiments 2-16, wherein M is Zr.

Embodiment 19

The compound defined in any one of embodiments 2-16, wherein M is Hf.

Embodiment 20

The compound defined in any one of embodiments 2-19, wherein each Xindependently is any monoanionic ligand disclosed herein.

Embodiment 21

The compound defined in any one of embodiments 2-20, wherein each Xindependently is H, BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁to C₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ toC₃₆ hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group.

Embodiment 22

The compound defined in any one of embodiments 2-21, wherein each Xindependently is any halide or C₁ to C₁₈ hydrocarbyl group disclosedherein.

Embodiment 23

The compound defined in any one of embodiments 2-22, wherein each X isCl.

Embodiment 24

A catalyst composition comprising the metallocene compound defined inany one of embodiments 2-23, an activator, and an optional co-catalyst.Embodiment 25. The composition defined in embodiment 24, wherein theactivator comprises any activator disclosed herein.

Embodiment 26

The composition defined in embodiment 24 or 25, wherein the activatorcomprises an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, or any combination thereof.

Embodiment 27

The composition defined in any one of embodiments 24-26, wherein theactivator comprises an aluminoxane compound.

Embodiment 28

The composition defined in any one of embodiments 24-26, wherein theactivator comprises an organoboron or organoborate compound.

Embodiment 29

The composition defined in any one of embodiments 24-26, wherein theactivator comprises an ionizing ionic compound.

Embodiment 30

The composition defined in embodiment 24 or 25, wherein the activatorcomprises an activator-support, the activator-support comprising anysolid oxide treated with any electron-withdrawing anion disclosedherein.

Embodiment 31

The composition defined in embodiment 30, wherein the solid oxidecomprises any solid oxide disclosed herein, e.g., silica, alumina,silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises any electron-withdrawing aniondisclosed herein, e.g., sulfate, bisulfate, fluoride, chloride, bromide,iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, or any combination thereof.

Embodiment 32

The composition defined in embodiment 30, wherein the activator-supportcomprises fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or any combination thereof.

Embodiment 33

The composition defined in embodiment 30, wherein the activator-supportcomprises fluorided alumina, sulfated alumina, fluorided silica-alumina,sulfated silica-alumina, fluorided silica-coated alumina, sulfatedsilica-coated alumina, or any combination thereof.

Embodiment 34

The composition defined in embodiment 30, wherein the activator-supportcomprises a fluorided solid oxide, a sulfated solid oxide, or anycombination thereof.

Embodiment 35

The composition defined in embodiment 30, wherein the activator-supportfurther comprises any metal or metal ion disclosed herein, e.g., zinc,nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten,molybdenum, zirconium, or any combination thereof.

Embodiment 36

The composition defined in embodiment 24 or 25, wherein the activatorcomprises an activator-support, the activator-support comprising a claymineral, a pillared clay, an exfoliated clay, an exfoliated clay gelledinto another oxide matrix, a layered silicate mineral, a non-layeredsilicate mineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, or any combination thereof.

Embodiment 37

The composition defined in any one of embodiments 24-36, wherein thecatalyst composition comprises a co-catalyst, e.g., any co-catalystdisclosed herein.

Embodiment 38

The composition defined in any one of embodiments 24-37, wherein theco-catalyst comprises an organoaluminum compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof.

Embodiment 39

The composition defined in any one of embodiments 24-38, wherein theco-catalyst comprises an organoaluminum compound.

Embodiment 40

The composition defined in embodiment 39, wherein the organoaluminumcompound comprises any organoaluminum compound disclosed herein, e.g.,trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., orcombinations thereof.

Embodiment 41

The composition defined in any one of embodiments 30-40, wherein thecatalyst composition is substantially free of aluminoxane compounds,organoboron or organoborate compounds, ionizing ionic compounds, orcombinations thereof.

Embodiment 42

The composition defined in any one of embodiments 30-40, wherein theco-catalyst comprises an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organoaluminumcompound, an organozinc compound, an organomagnesium compound, anorganolithium compound, or any combination thereof.

Embodiment 43

The composition defined in any one of embodiments 24-42, wherein thecatalyst composition comprises any metallocene compound having formula(I) disclosed herein.

Embodiment 44

The composition defined in any one of embodiments 24-43, wherein thecatalyst composition comprises only one metallocene compound havingformula (I).

Embodiment 45

The composition defined in any one of embodiments 24-44, wherein thecatalyst composition is produced by a process comprising contacting themetallocene compound and the activator.

Embodiment 46

The composition defined in any one of embodiments 24-45, wherein thecatalyst composition is produced by a process comprising contacting, inany order, the metallocene compound, the activator, and the co-catalyst.

Embodiment 47

The composition defined in any one of embodiments 24-46, wherein acatalyst activity of the catalyst composition is in any range disclosedherein, e.g., greater than about 75,000 grams, greater than about100,000 grams, greater than about 150,000 grams, greater than about200,000 grams, etc., of ethylene copolymer per gram of metallocenecompound per hour, under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as a diluent and1-hexene as a comonomer, and with a polymerization temperature of 80° C.and a reactor pressure of 400 psig.

Embodiment 48

An olefin polymerization process, the process comprising contacting thecatalyst composition defined in any one of embodiments 24-47 with anolefin monomer and an optional olefin comonomer in a polymerizationreactor system under polymerization conditions to produce an olefinpolymer.

Embodiment 49

The process defined in embodiment 48, wherein the olefin monomercomprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀ olefin.Embodiment 50. The process defined in embodiment 48 or 49, wherein theolefin monomer and the optional olefin comonomer independently comprisea C₂-C₂₀ alpha-olefin.

Embodiment 51

The process defined in any one of embodiments 48-50, wherein the olefinmonomer comprises ethylene.

Embodiment 52

The process defined in any one of embodiments 48-51, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Embodiment 53

The process defined in any one of embodiments 48-52, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Embodiment 54

The process defined in any one of embodiments 48-50, wherein the olefinmonomer comprises propylene.

Embodiment 55

The process defined in any one of embodiments 48-54, wherein thepolymerization reactor system comprises a batch reactor, a slurryreactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Embodiment 56

The process defined in any one of embodiments 48-55, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Embodiment 57

The process defined in any one of embodiments 48-56, wherein thepolymerization reactor system comprises a loop slurry reactor.

Embodiment 58

The process defined in any one of embodiments 48-57, wherein thepolymerization reactor system comprises a single reactor.

Embodiment 59

The process defined in any one of embodiments 48-57, wherein thepolymerization reactor system comprises 2 reactors.

Embodiment 60

The process defined in any one of embodiments 48-57, wherein thepolymerization reactor system comprises more than 2 reactors.

Embodiment 61

The process defined in any one of embodiments 48-60, wherein the olefinpolymer comprises any olefin polymer disclosed herein.

Embodiment 62

The process defined in any one of embodiments 48-61, wherein the olefinpolymer is an ethylene homopolymer, an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

Embodiment 63

The process defined in any one of embodiments 48-62, wherein the olefinpolymer is an ethylene/1-hexene copolymer.

Embodiment 64

The process defined in any one of embodiments 48-61, wherein the olefinpolymer is a polypropylene homopolymer or a propylene-based copolymer.

Embodiment 65

The process defined in any one of embodiments 48-64, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 60° C. to about 120° C. and a reaction pressure ina range from about 200 to about 1000 psig (about 1.4 to about 6.9 MPa).

Embodiment 66

The process defined in any one of embodiments 48-65, wherein thepolymerization conditions are substantially constant, e.g., for aparticular polymer grade.

Embodiment 67

The process defined in any one of embodiments 48-66, wherein no hydrogenis added to the polymerization reactor system.

Embodiment 68

The process defined in any one of embodiments 48-66, wherein hydrogen isadded to the polymerization reactor system.

Embodiment 69

The process defined in any one of embodiments 48-68, wherein the olefinpolymer (e.g., an ethylene/1-hexene copolymer) has a decrease in densityin any range disclosed herein, based on an increase in comonomer:monomermolar ratio (e.g., 1-hexene:ethylene molar ratio) from 0.6:1 to 1.2:1,e.g., a decrease in density of at least about 0.005 g/cm³ (up to about0.03 g/cm³), at least about 0.01 g/cm³, at least about 0.015 g/cm³, atleast about 0.02 g/cm³, etc.

Embodiment 70

The process defined in any one of embodiments 48-69, wherein thepolymerization reactor system comprises a loop slurry reactor, and thereis no fouling in the loop slurry reactor at an olefin copolymer densityof less than about 0.918, less than about 0.91, less than about 0.90g/cm³, etc.

Embodiment 71

The process defined in any one of embodiments 48-70, wherein the olefinpolymer has a density in any range disclosed herein, e.g., from about0.87 to about 0.96, from about 0.87 to about 0.94, from about 0.88 toabout 0.93, from about 0.89 to about 0.93, from about 0.895 to about0.925, from about 0.90 to about 0.92 g/cm³, etc.

Embodiment 72

The process defined in any one of embodiments 48-71, wherein the olefinpolymer has less than about 0.01 long chain branches (LCB) per 1000total carbon atoms, e.g., less than about 0.008 LCB per 1000 totalcarbon atoms, less than about 0.005 LCB per 1000 total carbon atoms,less than about 0.003 LCB per 1000 total carbon atoms, etc.

Embodiment 73

The process defined in any one of embodiments 48-72, wherein the olefinpolymer has a ratio of Mw/Mn in any range disclosed herein, e.g., fromabout 2 to about 6, from about 2 to about 5, from about 3 to about 6,from about 3 to about 5, etc.

Embodiment 74

The process defined in any one of embodiments 48-73, wherein the olefinpolymer has a conventional comonomer distribution, e.g., the number ofshort chain branches (SCB) per 1000 total carbon atoms at Mn is greaterthan Mw and/or the number of SCB per 1000 total carbon atoms at Mn isgreater than at Mz, etc.

Embodiment 75

The process defined in any one of embodiments 48-74, wherein the olefinpolymer has a melt index (MI) in any range disclosed herein, e.g.,greater than or equal to about 10, greater than or equal to about 25,greater than or equal to about 50, from about 50 to about 2000, fromabout 100 to about 1500, from about 25 to about 1000, from about 35 toabout 250 g/10 min, etc.

Embodiment 76

The process defined in any one of embodiments 48-75, wherein the olefinpolymer has a Mw in any range disclosed herein, e.g., from about 16,000to about 60,000, from about 20,000 to about 55,000, from about 18,000 toabout 50,000, from about 20,000 to about 50,000, from about 20,000 toabout 45,000, from about 25,000 to about 40,000 g/mol, etc.

Embodiment 77

The process defined in any one of embodiments 48-76, wherein the olefinpolymer has a Mn in any range disclosed herein, e.g., from about 3,000to about 20,000, from about 3,000 to about 18,000, from about 4,000 toabout 16,000, from about 4,000 to about 15,000, from about 3,500 toabout 13,500 g/mol, etc.

Embodiment 78

The process defined in any one of embodiments 48-77, wherein the olefinpolymer has a unimodal molecular weight distribution.

Embodiment 79

The process defined in any one of embodiments 69-78, wherein no hydrogenis added to the polymerization reactor system, e.g., the catalystcompositions and polymerization processes disclosed herein are capableof producing olefin polymers, with their respective polymer propertiesand characteristics, in the absence of added hydrogen.

Embodiment 80

An olefin polymer (e.g., an ethylene copolymer) produced by the olefinpolymerization process defined in any one of embodiments 48-79.

Embodiment 81

An article comprising the olefin polymer defined in embodiment 80.

Embodiment 82

A method or forming or preparing an article of manufacture comprising anolefin polymer, the method comprising (i) performing the olefinpolymerization process defined in any one of embodiments 48-79 toproduce an olefin polymer, and (ii) forming the article of manufacturecomprising the olefin polymer, e.g., via any technique disclosed herein.

Embodiment 83

The article defined in any one of embodiments 81-82, wherein the articleis an agricultural film, an automobile part, a bottle, a drum, a fiberor fabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, or atoy.

1-6. (canceled)
 7. A catalyst composition comprising a metallocenecompound, an activator, and an optional co-catalyst, wherein themetallocene compound has the formula:

wherein: M is Ti, Zr, or Hf; each X independently is a monoanionicligand; In^(A) is an indenyl group with an alkenyl substituent; In^(B)is an indenyl group; and each R independently is H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group.
 8. Thecomposition of claim 7, wherein the activator comprises an aluminoxanecompound, an organoboron or organoborate compound, an ionizing ioniccompound, or any combination thereof.
 9. The composition of claim 7,wherein the activator comprises an activator-support, theactivator-support comprising a solid oxide treated with anelectron-withdrawing anion.
 10. A metallocene compound having theformula:

wherein: M is Ti, Zr, or Hf; each X independently is a monoanionicligand; In^(A) is an indenyl group with an alkenyl sub stituent; In^(B)is an indenyl group; and each R independently is H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group.
 11. Thecompound of claim 10, wherein: M is Zr or Hf; each X independently is ahalide or a C₁ to C₁₈ hydrocarbyl group; and each R independently is Hor a C₁ to C₁₈ hydrocarbyl group.
 12. The compound of claim 10, whereinIn^(A) is an indenyl group with only an alkenyl sub stituent, and In^(B)is an indenyl group that does contain a sub stituent. 13-20. (canceled)21. The compound of claim 10, wherein In^(A) is an indenyl group withonly an alkenyl sub stituent, and In^(B) is an indenyl group that doesnot contain a sub stituent.
 22. The compound of claim 10, wherein each Rindependently is a C₁ to C₆ linear or branched alkyl group.
 23. Thecompound of claim 10, wherein In^(B) is an indenyl group with a C₁ to C₆linear or branched alkyl substituent.
 24. The compound of claim 10,wherein the alkenyl substituent is a C₃ to C₈ terminal alkenyl group.25. The compound of claim 10, wherein: M is Zr or Hf; each X is Cl;In^(A) is an indenyl group with a C₃ to C₈ terminal alkenyl substituent;and each R independently is H or a C₁ to C₈ hydrocarbyl group.
 26. Thecompound of claim 25, wherein each R independently is a C₁ to C₆ linearor branched alkyl group.
 27. The compound of claim 26, wherein: In^(A)is an indenyl group with only an alkenyl substituent; and each Rindependently is H or a C₁ to C₁₈ hydrocarbyl group.
 28. The compositionof claim 7, wherein: the catalyst composition comprises anorganoaluminum co-catalyst; and the activator comprises a fluoridedsolid oxide and/or a sulfated solid oxide.
 29. The composition of claim7, wherein In^(B) has a substituent selected from H, a halide, a C₁ toC₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group. 30.The composition of claim 7, wherein the activator comprises analuminoxane compound.
 31. The composition of claim 30, wherein: M is Zror Hf; each X independently is a halide or a C₁ to C₁₈ hydrocarbylgroup; and each R independently is H or a C₁ to C₁₈ hydrocarbyl group.32. The composition of claim 31, wherein: each X is Cl; In^(A) is anindenyl group with a C₃ to C₈ terminal alkenyl substituent; and each Rindependently is C₁ to C₆ linear or branched alkyl group.
 33. Thecomposition of claim 7, wherein the activator comprises fluoridedalumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-coated alumina, sulfated silica-coatedalumina, or any combination thereof.
 34. The composition of claim 7,wherein: In^(A) is an indenyl group with only an alkenyl substituent;and each R independently is H or a C₁ to C₁₈ hydrocarbyl group.
 35. Thecomposition of claim 34, wherein: M is Zr or Hf; In^(B) is an indenylgroup with one substituent; each X independently is a halide or a C₁ toC₁₈ hydrocarbyl group; and each R independently is C₁ to C₆ linear orbranched alkyl group.
 36. The composition of claim 34, wherein: each Xis Cl; and the alkenyl substituent is a C₃ to C₈ terminal alkenyl group.